腐食合成法に関する基礎的研究

• Material Type: 博士論文
• Title: 腐食合成法に関する基礎的研究
• Author/Editor: 佐々木, 大地
• Author Heading: 佐々木, 大地
• Publication Date: 2014-03-24
• Publication Date (W3CDTF): 2014-03-24
• Degree grantor/type: 室蘭工業大学
• Date Granted: 2014-03-24
• Date Granted (W3CDTF): 2014-03-24
• Dissertation Number: 甲第356号
• Degree Type: 博士（工学）
• Conferring No. (Dissertation): 甲第356号
• Text Language Code: jpn
• Alias of Author: SASAKI, Daichi
• NDC: 563
• Target Audience: 一般
• Note (General): application/pdf; 近年の工業社会における多機能化，高性能化，小型化というニーズに応えるべく，「安く」，「簡便に」，「微細で」，「高純度な」セラミックス粉末材料が求められている。申請者が研究している「腐食合成法」は自然腐食反応を利用した省エネルギー型の技術であり，新しい無機合成法の1つとして提案した。しかし本合成法は発案されて新しく，詳細な手法の確立が成されていない。そのため金属による腐食条件の適応性，合成可能な複酸化物の種類を調査・整理といった基礎的な研究を行う意義があると考えられる。本論文は，酸性溶液の腐食現象を利用しアルミニウム系複酸化物を，錯体溶液中でチタン系複酸化物を，また難腐食性金属は電解を用いて合成を試みて適用例を示すと共に，腐食合成法の特徴，並びに法則性を腐食防食学の観点よりまとめたものである。まずスピネルMgAl2O4の作製を例にとり，電位-pH図を用いた腐食から合成までの作製方針とその過程での反応を腐食合成法の原理としてまとめ，それを基にした出発原料の選択，実験装置とその手順を腐食合成法の方法としてまとめた。上記方針並びに方法に沿って，スピネル，コーディエライトMg2Al4Si5O18，コバルトスピネルCoAl2O4，亜鉛スピネルZnAl2O4，ニッケルスピネルNiAl2O4，マンガンスピネルMnAl2O4をアルコール中における腐食反応を利用して作製した。またチタン酸ストロンチウムSrTiO3，チタン酸バリウムBaTiO3，チタン酸ニッケルNiTiO3，チタン酸コバルトCoTiO3をチタンの過酸化水素水とアンモニア水の混合溶液における溶解（錯体化）を利用して作製した。また塩化物無添加の酸性水溶液中におけるアルミニウム電極の陽極溶解を用いてアルミン酸リチウムLiAlO2を作製した。XRD，粒度分布，SEM観察結果と共に腐食合成法の適用例を示した。研究を通じて，出発原料によっては金属の腐食反応が進み難い組み合わせが存在することが判明し，それは腐食防食学の援用により予想できることが明らかとなった。腐食合成法は，作製が簡単で高純度の複酸化物粉末が期待できるが，生産には耐食設備が必須であり，pH調整時には注意点があるといった，長所と短所を明らかにした。以上から腐食反応を用いてセラミックス粉末材料を作製する腐食合成法は。簡易的で省エネ型の技術であり，新しい無機合成法の１つとして提案できると結論した。; Corrosion synthesis proposed here is studied as one of the new inorganic synthesis. Application and its limitation of this theory are not described in detail. From the electrochemical point of view, it is needed to find the necessary (thermodynamics) and sufficient (reaction ratio) condition of the corrosion reaction between metals and solutions. From the physical point of view, it is necessary to express properties and characteristics of powders obtained by the corrosion synthesis. In this study, three ways were carried out: ①preparation of aluminum-based double oxide by corrosion reaction in acid solution, ②preparation of titanium-based double oxide by dissolution reaction in mixed solution (hydrogen peroxide and ammonium hydroxide), ③synthesis by anodic dissolution reaction of metal which is hardly dissolved. Pourbaix diagrams of magnesium and aluminum were applied to guide for obtaining spinel (MgAl2O4). It was found that metallic magnesium was dissolved in acid solution faster than aluminum. Chloride ions were added to the solution as catalyst to attack magnesium more quickly. The corrosion product obtained was hydrolyzed and then fired. The sintered powders of spinel were characterized by XRD, measured particle size distribution, and observed particle surface and morphology. According to the principle and the methods above, cordierite (Mg2Al4Si5O18), cobalt spinel (CoAl2O4), zinc aluminate spinel (ZnAl2O4), nickel aluminate spinel (NiAl2O4), and manganese aluminate spinel (MnAl2O4) were prepared by corrosion phenomenon in alcohol. Strontium titanate (StTiO3), barium titanate (BaTiO3), nickel titanate (NiTiO3), and cobalt titanate (CoTiO3) were preparedby dissolved in acid solution faster than aluminum. Chloride ions were added to the solution as catalyst to attack magnesium more quickly. The corrosion product obtained was hydrolyzed and then fired. The sintered powders of spinel were characterized by XRD, measured particle size distribution, and observed particle surface and morphology. According to the principle and the methods above, cordierite (Mg2Al4Si5O18), cobalt spinel (CoAl2O4), zinc aluminate spinel (ZnAl2O4), nickel aluminate spinel (NiAl2O4), and manganese aluminate spinel (MnAl2O4) were prepared by corrosion phenomenon in alcohol. Strontium titanate (StTiO3), barium titanate (BaTiO3), nickel titanate (NiTiO3), and cobalt titanate (CoTiO3) were prepared by dissolution reaction of metallic titanium in solution with mixture of hydrogen peroxide and ammonium hydroxide. Lithium aluminate (LiAlO2) was prepared by anodic dissolution reaction of aluminum in acid solution without chloride ion. Experiments and considerations above lead that corrosion synthesis has some merits and demerits. The merits are as follows: ①this synthesis is easy preparation process and energy saving process, ②high purity double oxide is obtained, ③it is possible to understand quantitatively and controlled in detailed by applying corrosion science and technology. On the other hand, the demerits are as follows: ④corrosion resistance materials are necessary, ⑤good timing pH adjusting is needed. It is concluded that corrosion synthesis for preparing nano-materials for ceramic powders is easy and low-cost method, and can be proposed as one of the new inorganic synthesis.
• DOI: 10.15118/00005111; https://doi.org/10.15118/00005111
• Persistent ID (NDL): info:ndljp/pid/9921529; https://dl.ndl.go.jp/pid/9921529
• Collection: 障害者向け資料
• Collection (Materials For Handicapped People:1): テキストデータ
• Collection (particular): 国立国会図書館デジタルコレクション > デジタル化資料 > 博士論文; https://dl.ndl.go.jp/collections/A00014
• Acquisition Basis: 博士論文（自動収集）
• Date Accepted (W3CDTF): 2016-04-01T14:32:40+09:00
• Date Created (W3CDTF): 2016-02-15
• Format (IMT): application/pdf
• Access Restrictions: 国立国会図書館内限定公開
• Service for the Digitized Contents Transmission Service: 図書館・個人送信対象外
• Availability of remote photoduplication service: 可
• Periodical Title (URI): http://dx.doi.org/10.15118/00005111; http://hdl.handle.net/10258/3446; https://muroran-it.repo.nii.ac.jp/records/5120
• Data Provider (Database): 国立国会図書館 : 国立国会図書館デジタルコレクション; https://dl.ndl.go.jp